CN106166499B - A kind of method that catalytic cellulose conversion prepares 5 hydroxymethyl furfural in green solvent system - Google Patents
A kind of method that catalytic cellulose conversion prepares 5 hydroxymethyl furfural in green solvent system Download PDFInfo
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- CN106166499B CN106166499B CN201610596666.7A CN201610596666A CN106166499B CN 106166499 B CN106166499 B CN 106166499B CN 201610596666 A CN201610596666 A CN 201610596666A CN 106166499 B CN106166499 B CN 106166499B
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 87
- 239000001913 cellulose Substances 0.000 title claims abstract description 39
- 229920002678 cellulose Polymers 0.000 title claims abstract description 39
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 38
- 239000002904 solvent Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 26
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims description 58
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims description 55
- 239000003054 catalyst Substances 0.000 claims abstract description 60
- 108090000790 Enzymes Proteins 0.000 claims abstract description 42
- 102000004190 Enzymes Human genes 0.000 claims abstract description 42
- 229940088598 enzyme Drugs 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000126 substance Substances 0.000 claims abstract description 37
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 36
- 239000008103 glucose Substances 0.000 claims abstract description 34
- 239000000835 fiber Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002808 molecular sieve Substances 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006731 degradation reaction Methods 0.000 claims abstract description 14
- 108010059892 Cellulase Proteins 0.000 claims abstract description 13
- 229940106157 cellulase Drugs 0.000 claims abstract description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 38
- 239000000047 product Substances 0.000 claims description 32
- 238000001291 vacuum drying Methods 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 238000005119 centrifugation Methods 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 230000015556 catabolic process Effects 0.000 claims description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 10
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 230000001476 alcoholic effect Effects 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 239000002608 ionic liquid Substances 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 5
- 239000002356 single layer Substances 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- DEOPWJHDYPLPRX-UHFFFAOYSA-M iron chloride hydrate Chemical compound O.[Cl-].[Fe] DEOPWJHDYPLPRX-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 150000003754 zirconium Chemical class 0.000 claims description 2
- 244000248349 Citrus limon Species 0.000 claims 1
- 235000005979 Citrus limon Nutrition 0.000 claims 1
- 230000003139 buffering effect Effects 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 239000002028 Biomass Substances 0.000 abstract description 6
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract description 2
- CETXOEGRUBXUAL-UHFFFAOYSA-N 3-(hydroxymethyl)furan-2-carbaldehyde Chemical class OCC=1C=COC=1C=O CETXOEGRUBXUAL-UHFFFAOYSA-N 0.000 abstract 1
- 235000015165 citric acid Nutrition 0.000 description 12
- 229930091371 Fructose Natural products 0.000 description 6
- 239000005715 Fructose Substances 0.000 description 6
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000003301 hydrolyzing effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000186216 Corynebacterium Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 108700040099 Xylose isomerases Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000033772 system development Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/003—Catalysts comprising hydrides, coordination complexes or organic compounds containing enzymes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/14—Enzymes or microbial cells immobilised on or in an inorganic carrier
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- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P17/00—Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms
- C12P17/02—Oxygen as only ring hetero atoms
- C12P17/04—Oxygen as only ring hetero atoms containing a five-membered hetero ring, e.g. griseofulvin, vitamin C
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Abstract
The invention belongs to biomass catalyzing field, a kind of method that catalytic cellulose conversion prepares 5 hydroxymethylfurfurals in green solvent system is provided.Based on silicon-based mesoporous molecular sieve SBA 15, it is prepared for magnetic carrier Fe3O4@SBA 15, and prepare biological enzyme agent cellulase Fe for carrying fiber element enzyme3O4@SBA‑15；Load ZrO2/SO4 2‑Type solid super-strong acid is successfully prepared 15 chemical catalysts of 2SZ@SBA.It is coupled this two classes catalyst, realizes that biological enzyme agent efficient catalytic degraded cellulose obtains glucose in aqueous solution, in the mixed solution of isopropanol/water, the glucose that chemical catalyst catalytic degradation reaction obtains prepares 5 HMF.Efficient Conversion of the cellulose to 5 HMF in the achievable green solvent system of series connection of two-step catalysis reaction.
Description
Technical field
The present invention relates to novel catalytic reaction system development field, it is related specifically to cellulose in a kind of green solvent system
The method that catalyzed conversion prepares 5 hydroxymethyl furfural (5-HMF), meanwhile, this method can be extended to a series of biomass of catalysis
Conversion prepares 5-HMF.
Background technology
5 hydroxymethyl furfural (5-hydroxymethylfurfural, 5-HMF) is to contain active aldehyde in a kind of structural formula
The biomass-based platform chemicals of base, hydroxyl and furan nucleus can derive numerous downstream product by further reacting,
It is the key intermediate for connecting biomass chemistry and petrochemistry.It is presently used for preparing the biomass-based carbohydrate of 5-HMF
Include mainly fructose, glucose and cellulose.It is wherein, although higher as raw material preparation 5-HMF yields using fructose and glucose,
Expensive raw material price, while certain competition is largely generated to food supply using edibility fructose and glucose.Therefore, with
Cheap, resourceful cellulose efficiently prepares 5-HMF for raw material becomes current research hotspot.
The macromolecular linear polymer that cellulose is made of D-Glucose with β-Isosorbide-5-Nitrae glycosidic bond, intermolecular there are huge
Hyarogen-bonding, difficulty is dissolved in common solvent.In recent years, be composed entirely of ions at normal temperatures, in principle can be unlimited
A kind of green organic solvent-ionic liquid (Ionic Liquids, ILs) of recycling, shows cellulose good
Solvability, thus received significant attention in biomass conversion field.In ILs dicyandiamide solutions, prepared by catalytic conversion of cellulose
5-HMF is mainly concerned with following reaction：(1) cellulose is degraded to fiber oligomer in ionic liquid；(2) fiber oligomer water
Solution is glucose；(3) glucose isomerase turns to fructose and the dehydration of (4) fructose generates 5-HMF.Fiber oligomer hydrolyzes and fructose is de-
Being smoothed out for water reaction needsThe presence of acidic site, and glucose isomerization process has generally required alkalinity
Or the presence of Lewis acidic sites.Therefore, so complicated reaction step is faced, how effectively to realize turning for cellulose
Change, improves the selectivity of reaction process and the yield of 5-HMF, be a very challenging project.In general, using string
Join multistep catalysis reaction, required catalyst is added in the reaction that each step is related to, it can be achieved that cellulose Efficient Conversion,
Obtain the 5-HMF of higher yields.But the ILs or highly polar aprotic solvent of this kind of reaction system generally use costliness, it leads
Cause catalyst separation regeneration used in often step difficult, stability is low, and the obtained 5-HMF separating and extractings of reaction are difficult, instead
System is answered to be difficult to realize greenization.
Invention content
The object of the present invention is to provide in a kind of green solvent system, biological enzyme agent and chemical catalyst combination are catalyzed
Cellulose converts the method for preparing 5-HMF.Choose load Fe3O4The silicon-based mesoporous molecular sieve SBA-15 of nano-particle is magnetic carries
Body, anchoring fiber element enzyme obtain biological enzyme agent；Using the alkoxide of zirconium as presoma, by hydrolysis and vulcanization reaction, by ZrO2/
SO4 2-Type solid super-strong acid is supported on SBA-15, prepares chemical catalyst.Two kinds of catalyst are respectively used to be catalyzed drop in aqueous solution
The glucose that is obtained to catalytic conversion reaction in the mixed system of glucose and alcoholic solvent/water of solution cellulose obtains 5-HMF, and two
Efficient Conversion of the cellulose to 5-HMF in achievable green solvent system that be together in series is reacted in step catalysis.
The technical solution adopted by the present invention is：
A kind of method that catalytic cellulose conversion prepares 5 hydroxymethyl furfural in green solvent system, includes the following steps：
A, the preparation of biological enzyme agent：
A1, in proportion by iron chloride hydrate (FeCl3·6H2O it) is added in ethylene glycol with sodium acetate (NaAc), ultrasound
Form uniformly mixed solution；Then it takes the silicon-based mesoporous molecular sieve SBA-15 after drying to be dispersed in above-mentioned solution, is stirring
Under conditions of, polyethylene glycol (PEG) is added dropwise into mixed system, solution after mixing is added in autoclave instead
It answers, after reaction, obtained solid is washed through water and ethyl alcohol, is collected by centrifugation, and is dried in vacuo, and obtains loading the Fe that is magnetic3O4's
SBA-15(Fe3O4@SBA-15)；
A2, Fe obtained by step (1) is taken3O4@SBA-15 are dispersed in citric acid solution, after mixing, in stirring
Under the conditions of into mixed system be added cellulase (cellulase), reaction system realizes cellulase at a certain temperature
Load, for product through being collected by centrifugation, vacuum drying obtains biological enzyme agent (cellulase-Fe3O4@SBA-15)。
In step A1, described SBA-15, FeCl3·6H2O, NaAc, PEG, ethylene glycol ratio be 0.2-10g：0.1-
6.5g：1-40g：0.4-20g：30-200mL；Reaction temperature is 100-300 DEG C, reaction time 6-48h；Vacuum drying temperature
Degree is 40-120 DEG C.
In step A2, the citric acid solution pH ranging from 2.0-4.8.
In step A2, the Fe3O4@SBA-15, cellulase, citric acid solution ratio be 10-100mg：
0.4-5.0mg：1-10mL；Reaction temperature is 0-10 DEG C, reaction time 12-96h；Vacuum drying temperature is 20-50 DEG C.
B, the preparation of chemical catalyst：
B1, take it is dry after silicon-based mesoporous molecular sieve SBA-15 dispersion in organic solvent, under stirring conditions, to mixed
Hydrolyzable zirconium salt solution is added dropwise in zoarium system, after reaction system hydrolysis is complete, products therefrom is washed, centrifugation is received
Collection, vacuum drying obtain the zirconium oxide product (1ML-ZrO of SBA-15 load single layers2@SBA-15)；
B2,1ML-ZrO obtained by step (1) is taken2Silicon-based mesoporous molecular sieve SBA-15 in@SBA-15 alternative steps (1) repeats
Hydrolysis in step (1) obtains the zirconium oxide product (2ML-ZrO that SBA-15 loads two layers2@SBA-15)；
B3, by the 2ML-ZrO obtained by step (2)2@SBA-15 are immersed in sulfuric acid solution, and after immersion, centrifugation is received
Collect product, vacuum drying is placed in Muffle furnace, temperature programming to calcination temperature, and calcining obtains the 2ML- of SBA-15 loads
ZrO2/SO4 2-Type solid super-strong acid (2SZ@SBA-15)；
In step B1, the organic solvent is n-hexane, hexamethylene, normal propyl alcohol or isopropanol；Hydrolyzable zirconates is positive third
Alcohol zirconium or zirconium iso-propoxide.
In step B1, the SBA-15, hydrolyzable zirconates, organic solvent ratio be 0.2-10g：1.0-58.5g：10-
600mL；Hydrolysising reacting temperature is 50-120 DEG C, reaction time 6-48h；Vacuum drying temperature is 40-120 DEG C.
In step B2, the 1ML-ZrO2@SBA-15, hydrolyzable zirconates, organic solvent ratio be 0.2-10g：0.6-
28.5g：10-600mL, hydrolysising reacting temperature are 50-120 DEG C, reaction time 6-48h；Vacuum drying temperature is 40-120
℃。
In step B3, the concentration range of the sulfuric acid solution is 0.005-0.25mol/L.
In step B3, the 2ML-ZrO2@SBA-15, sulfuric acid solution ratio be 0.2-1.8g：10-90mL, when immersion
Between be 4-24h；Vacuum drying temperature is 60-150 DEG C；Heating rate is 1.0-10 DEG C/min, calcination temperature 400-1200
DEG C, calcination time 1-10h.
C, chemical catalyst made from biological enzyme agent made from step A and step B is degraded applied to sequential catalyst
Cellulose prepares the reaction of 5-HMF：
C1, biological enzyme agent cellulase-Fe3O4The step of@SBA-15 catalytic degradation fiber monomers obtain glucose：
Cellulose is handled first to obtain fiber monomer through ionic liquid, then in proportion delays fiber monomer and citric acid
It rushes solution to be uniformly mixed, adds biological enzyme agent cellulase-Fe3O4@SBA-15 made from step A, catalytic degradation is fine
Dimension monomer obtains glucose；
C2, reaction product obtained by step C1 is detached into biological enzyme agent by externally-applied magnetic field active force, obtains reaction newly
System；
The step of C3, chemical catalyst 2SZ@SBA-15 catalytic degradation glucose prepare 5-HMF：
A certain amount of alcoholic solvent will be added in reaction system obtained by step C2, after system temperature rises to required temperature,
Chemical catalyst made from step B is added, reaction terminates, and obtains 5-HMF.
In step C1, the temperature of the pH=3.6-6.0 of the citric acid solution, reaction system catalytic degradation are 20-
80 DEG C, time 12-48h.
In step C1, the fiber monomer, citric acid solution, biological enzyme agent cellulase-Fe3O4@SBA-
15 amount ratio is 20-100mg：1-10mL：20-100mg.
In step C3, the alcoholic solvent is normal propyl alcohol, isopropanol, n-butanol, isobutanol or the tert-butyl alcohol, temperature of reaction system
It is 80-180 DEG C, reaction time 4-12h.
The amount ratio of the alcoholic solvent, chemical catalyst 2SZ@SBA-15, step C2 gained reaction system solvents is 9-
90mL：20-100mg：1-10mL.
The advantage of the invention is that：
(1) in terms of catalyst property：First, the cellulase of biology catalytic activity will is fixed on magnetic Fe3O4@SBA-
Prepared biological enzyme agent cellulase-Fe on 153O4@SBA-15, the high catalysis reaction for not only maintaining biological enzyme are lived
Property, while the reuse of the catalyst may be implemented；Secondly, prepared chemical catalyst not only have superpower acidity (Acid and Lewis acid), while there is certain alkalinity, prepare 5-HMF in the obtained glucose of catalytic degradation reaction
In reaction processAcid site, the acid sites Lewis and basic site synergistic effect, considerably improve glucose
Isomerisation degree, the yield and selectivity of 5-HMF.Two class catalyst cascades use in the present invention, can effective catalytic degradation fiber
Element obtains the 5-HMF of higher yields.
(2) in terms of catalystic converter system：Biological enzyme agent cellulase-Fe3O4@SBA-15 catalytic degradation fiber monomers
The catalysis reaction for obtaining glucose carries out in acid aqueous solution, waits for after reaction, can by the active force of external magnetic field
Realize the separation of catalyst；The obtained glucose of subsequent chemistry catalyst 2SZ@SBA-15 catalytic degradation reactions prepares 5-HMF
Reaction process carries out in the green solvent of alcoholic solvent/water, can realize that product 5-HMF's efficiently separates purification after reaction.
Solvent used in two step cascade reaction systems is green renewable solvent in the present invention, in conjunction with the height catalysis of two class catalyst
Reactivity is, it can be achieved that Efficient Conversion of the cellulose to 5-HMF in green solvent system.
(3) present invention uses technology, and preparation process is simple, easy to operate, suitable for industrialized production.
Description of the drawings
Fig. 1 be embodiment 1 in prepared biological enzyme agent hysteresis loop figure (a, upper left side insert pictures be transmission electricity
Mirror figure, lower right insert pictures are Magneto separate design sketch) and Wide angle X-ray diffraction figure (b).
Scheme outside the solid violet of prepared biological enzyme agent in Fig. 2 embodiments 1.
Fig. 3 is the scanning electron microscope (a) and transmission electron microscope (b) figure of prepared chemical catalyst in embodiment 1.
Fig. 4 is wide-angle (a) He little Jiao (b) X-ray diffractograms of prepared chemical catalyst in embodiment 1.
Fig. 5 is the nitrogen adsorption desorption curve (a) of prepared sample in SBA-15 carriers and each step in embodiment 1
With graph of pore diameter distribution (b).
Fig. 6 is the xps energy spectrum figure of prepared sample in SBA-15 carriers and each step in embodiment 1.
Fig. 7 is the NH of prepared chemical catalyst in embodiment 13(a) and CO2(b) temperature programming desorbs attached drawing.
Fig. 8 is the infrared figure of pyridine in situ of prepared chemical catalyst in embodiment 1.
Specific implementation mode
Below in conjunction with the accompanying drawings and specific embodiment the present invention is further illustrated, but protection scope of the present invention is simultaneously
It is without being limited thereto.
Embodiment 1
(1) preparation of biological enzyme agent
By the FeCl of 0.1g3·6H2The NaAc of O and 1.0g is added in 30mL ethylene glycol, is ultrasonically formed uniformly mixed molten
Liquid；Then the silicon-based mesoporous molecular sieve SBA-15 after taking 0.2g to dry is dispersed in above-mentioned solution, under stirring conditions, to mixed
0.4g PEG are added dropwise in zoarium system, solution after mixing is added in autoclave, after reacting 6h at 100 DEG C,
Obtained solid is washed through water and ethyl alcohol, is collected by centrifugation, and obtains loading the Fe that is magnetic after 40 DEG C of vacuum drying3O4SBA-15
(Fe3O4@SBA-15)。
Take Fe obtained by 10mg previous steps3O4@SBA-15 are dispersed in 1mL, in the buffer solution of pH=2.0 citric acids, mixing
After uniformly, the cellulase of 0.4mg is added into mixed system under stirring conditions, reaction system reacts 12h at 0 DEG C
Afterwards, for products therefrom through being collected by centrifugation, 20 DEG C of vacuum drying obtain biological enzyme agent cellulase-Fe3O4@SBA-15。
(2) preparation of chemical catalyst
The silicon-based mesoporous molecular sieve SBA-15s of 0.2g after drying are dispersed in 10mL n-hexanes, under stirring conditions,
The zirconium-n-propylate of 1.0g is added dropwise into mixed system.Reaction system at 50 DEG C after hydrolyzing 6h, and products therefrom is through distillation
Water washing 3-5 times is collected by centrifugation and obtains the zirconium oxide product (1ML-ZrO that SBA-15 loads single layer with 40 DEG C of vacuum drying2@
SBA-15)。
1ML-ZrO obtained by 0.2g previous steps2@SBA-15 are dispersed in again in 10mL n-hexanes, under stirring conditions,
The zirconium-n-propylate of 0.6g is added dropwise into mixed system.Reaction system at 50 DEG C after hydrolyzing 6h, and products therefrom is through distillation
Water washing 3-5 times is collected by centrifugation and obtains the zirconium oxide product (2ML-ZrO that SBA-15 loads two layers with 40 DEG C of vacuum drying2@
SBA-15)。
By the 2ML-ZrO obtained by 0.2g previous steps2@SBA-15 are immersed in 10mL, in the sulfuric acid solution of 0.005mol/L,
It impregnates and centrifuges collected product after 4h and be placed in Muffle furnace through 60 DEG C of vacuum drying, with the heating rate of 1.0 DEG C/min from room
Temperature is increased to 400 DEG C, and keeps 1h at a temperature of 400 DEG C, obtains the 2ML-ZrO of SBA-15 loads2/SO4 2-Type solid super-strong acid
(2SZ@SBA-15)。
By magnetic carrier Fe prepared in Fig. 13O4Its magnetic intensity can be obtained in the hysteresis loop figure (a) of@SBA-15 is
60.5emu g-1, while being clear that a nanometer shape Fe from the transmission plot of insertion3O4The presence of particle, passes through externally-applied magnetic field
Active force, the magnetic carrier can be detached with mixed system easily.Meanwhile it can be seen that prepared in Wide angle X-ray diffraction figure (b)
Magnetic carrier Fe3O4There is Fe in@SBA-153O4The characteristic diffraction peak of nano particle, again demonstrates Fe3O4Success it is negative
It carries.
By scheme outside the solid violet of biological enzyme agent prepared in Fig. 2 it can be seen that it is in 280nm wavelength have it is ultraviolet
Absorption peak, it was demonstrated that cellulase is successfully supported on magnetic carrier Fe3O4On@SBA-15.
Can be seen that prepared chemical catalyst is corynebacterium by Fig. 3 scanning electron microscope (SEM) photographs, length is about 1 μm or so,
Diameter is about 360nm or so；It can clearly observe that solid catalyst surface distribution is a large amount of orderly from transmission electron microscope picture
Mesoporous, aperture is about 4.8nm or so.
There was only the spy of SBA-15 carriers by the chemical catalyst prepared by Wide angle X-ray diffraction it can be seen from the figure that in Fig. 4
Diffraction maximum is levied, loaded ZrO does not occur2Characteristic peak, this phenomenon may be the ZrO by being loaded2Gone out with colloidal state
It is existing, and particle very little, cause its characteristic peak to be difficult to be detected.Small angle X-ray diffraction figure proves prepared chemical catalyst
Meso-hole structure still remain the typical hexagonal symmetry of high-sequential.
In Fig. 5 (a), middle nitrogen adsorption desorption is attached to typical meso-hole structure, wherein SBA-15 carriers are in carried magnetic
Fe3O4Nano particle and ZrO2Afterwards, specific surface area has a degree of decline, meanwhile, graph of pore diameter distribution (b) also embodies
The decline rule in aperture in loading process.Finally, the prepared magnetic carrier Fe for loading biological enzyme3O4@SBA-15's
Specific surface area is 439.6cm2g-1, while its aperture integrated distribution is in 6.1nm or so；Prepared chemical catalyst specific surface area
For 268.8cm2g-1, while its aperture integrated distribution is in 4.9nm or so and the obtained result of transmission electron microscope observing basic one
It causes.
In figure 6, Fe3O4The appearance of Fe 2p signal peaks in the xps energy spectrum figure of@SBA-15, it was demonstrated that magnetic Fe3O4It receives
Rice grain is successfully supported on silicon-based mesoporous molecular sieve SBA-15；2ML-ZrO2Zr 3d signals in the xps energy spectrum figure of@SBA-15
The appearance at peak, it was demonstrated that ZrO2Successfully it is supported on SBA-15；By further sulfurization, S 2p signal peaks are demonstrate,proved
It is bright to be successfully prepared solid super-strong acid 2SZ@SBA-15 chemical catalysts.
(a) NH in Fig. 73And CO2(b) temperature programming desorption curve can calculate prepared chemical catalyst
Acidity value is 0.42mmol g-1, basicity value is 0.03mmol g-1, it was demonstrated that prepared 2SZ@SBA-15 chemical catalysts are one
Kind soda acid difunctionalization solid catalyst.
It is prepared it can be seen from the pyridine infrared spectrogram in situ of 2SZ@SBA-15 chemical catalysts in Fig. 8 to urge
Agent has bronsted acid (1542cm simultaneously-1) and lewis acid (1447cm-1) active site characteristic peak, it was demonstrated that this method
Contain B acid and L sour two kinds of acidic sites while prepared solid catalyst.The above characterization proves that the invention can succeed
A kind of solid catalyst acid, basic site containing B/L is prepared, the presence of L acidic sites and basic site can very great Cheng
The isomerization that glucose is improved on degree, to enhance catalyst activity.
(3) catalytic activity is tested, i.e. biological enzyme agent and chemical catalyst is applied to sequential catalyst degraded cellulose system
The reaction of standby 5-HMF：
It is fine in order to improve biological enzyme activity to a greater extent since there are a large amount of hydrogen bonds between cellulosic molecule
Dimension element first passes around the pretreatment of ionic liquid (1- butyl -3- methylimidazole villaumites), to destroy its intermolecular Hydrogen Bond Systems.
First, the cellulose crystals of 2g ionic liquid 1-butyl-3-methyl imidazoliums chlorine and 0.1g are added in the single-necked flask of 25mL,
System is in 120 DEG C of oil bath pan, and after reacting 1h under the rotating speed of 1200r/min, the methanol that 3mL is added promotes reaction to terminate, from
The heart is collected to obtain fiber monomer.Then, 1mL is added in 20mg fibers monomer, and the citric acid solution of pH=3.6 is uniformly mixed
Afterwards, the biological enzyme agent cellulase-Fe of 20mg is added into the system3O4@SBA-15, reaction system are reacted at 20 DEG C
12h.After reaction, biological enzyme agent is detached by externally-applied magnetic field active force, the different of 9mL is then added in the reaction system
The chemical catalyst of 20mg is added after system temperature rises to 80 DEG C in propyl alcohol, reacts 4h.The Portugal that fiber monomer is degraded
Grape sugar configures differential refraction detector with efficient liquid phase (HPLC) and nh 2 column is detected, and products therefrom constant volume is worked as to volumetric flask
In, after be diluted to 5000 times, testing conditions are：Column temperature：65℃；Mobile phase is 0.001M H2SO4；Flow velocity is 0.55mL/min；
Sample size is 20 μ L.Final products therefrom 5-HMF configures UV detector with HPLC and C18 columns are detected, and extension rate is same
Glucose.Testing conditions are：Column temperature：30℃；Mobile phase is water and methanol, ratio 3:7；Flow velocity is 0.7mL/min；Detect wave
A length of 283nm；Sample size is 20 μ L.
Glucose sample standard curve is y=3.3607x+207.2643, and 5-HMF sample standard curves are y=0.0019x
+ 3.4903 (y indicates that glucose or the corresponding concentration of 5-HMF, unit mg/L, x indicate peak areas), can be with according to standard curve
Glucose or the concentration of 5-HMF are calculated, molar concentration is converted into.Products collection efficiency calculation formula is Y (molar yield)=n1/no
× 100, n1Represent reaction gained glucose or the molar yield of 5-HMF, noRepresent contained glucose in reaction substrate cellulose
Mole.Result of calculation shows that product can reach higher yield, glucose yield 86.2%, and 5-HMF yields are 43.6%.
(4) regenerability is tested
In the present invention, the fast and effective separation of catalyst can be achieved by the effect of externally-applied magnetic field for biological enzyme agent, change
The recycling of chemical catalyst can by centrifugation, detach, be dried to obtain.The catalyst that two classes recycle is put into above-mentioned urge again
Change in experiment, tests its catalytic effect；Four regeneration tests are carried out in this approach.Measured catalysate detection method and examination
Condition is tested with above-mentioned catalytic test.
The result shows that：Loss of catalyst activity is relatively low in regenerative process, during regenerating one to five experiment, glucose
Yield is followed successively by 86.1%, 85.9%, 85.5%, 85.1%, the yield of 84.0%, 5-HMF be followed successively by 43.2%, 42.7%,
42.3%, 42.0% and 41.4%.
Embodiment 2
(1) preparation of biological enzyme agent
By the FeCl of 4.0g3·6H2The NaAc of O and 20g is added in 120mL ethylene glycol, is ultrasonically formed uniformly mixed molten
Liquid；Then the silicon-based mesoporous molecular sieve SBA-15 after taking 5.0g to dry is dispersed in above-mentioned solution, under stirring conditions, to mixed
10g PEG are added dropwise in zoarium system, solution after mixing is added in autoclave, after being reacted for 24 hours at 200 DEG C,
Obtained solid is washed through water and ethyl alcohol, is collected by centrifugation, and obtains loading the Fe that is magnetic after 80 DEG C of vacuum drying3O4SBA-15
(Fe3O4@SBA-15)。
Take Fe obtained by 50mg previous steps3O4@SBA-15 are dispersed in 5mL, in the buffer solution of pH=3.6 citric acids, mixing
After uniformly, the cellulase of 2.5mg is added into mixed system under stirring conditions, reaction system reacts 48h at 5 DEG C
Afterwards, for products therefrom through being collected by centrifugation, 35 DEG C of vacuum drying obtain biological enzyme agent cellulase-Fe3O4@SBA-15。
(2) preparation of chemical catalyst
The silicon-based mesoporous molecular sieve SBA-15s of 5.0g after drying are dispersed in 300mL n-hexanes, under stirring conditions,
The zirconium-n-propylate of 25g is added dropwise into mixed system.Reaction system at 80 DEG C after hydrolyzing 30h, and products therefrom is through distillation
Water washing 3-5 times is collected by centrifugation and obtains the zirconium oxide product (1ML-ZrO that SBA-15 loads single layer with 80 DEG C of vacuum drying2@
SBA-15)。
1ML-ZrO obtained by 5.0g previous steps2@SBA-15 are dispersed in again in 300mL n-hexanes, in the condition of stirring
Under, the zirconium-n-propylate of 15g is added dropwise into mixed system.Reaction system at 80 DEG C after hydrolyzing 30h, and products therefrom is through steaming
Distilled water washs 3-5 times, the zirconium oxide product (2ML-ZrO for being dried in vacuo with 80 DEG C and obtaining SBA-15 and loading two layers is collected by centrifugation2@
SBA-15)。
By the 2ML-ZrO obtained by 1.0g previous steps2@SBA-15 are immersed in 50mL, in the sulfuric acid solution of 0.1mol/L, leaching
Collected product is centrifuged after bubble 15h to be placed in Muffle furnace through 80 DEG C of vacuum drying, with the heating rate of 5.0 DEG C/min from room temperature
800 DEG C are increased to, and 5h is kept at a temperature of 800 DEG C, obtains the 2ML-ZrO of SBA-15 loads2/SO4 2-Type solid super-strong acid
(2SZ@SBA-15)。
(3) catalytic activity is tested, i.e. biological enzyme agent and chemical catalyst is applied to sequential catalyst degraded cellulose
Prepare the reaction of 5-HMF：
Cellulose pre-processes to obtain fiber monomer with embodiment 1 through ILs.5mL, pH is added in 50mg fiber monomers afterwards
The biological enzyme agent cellulase- of 50mg is added into the system after mixing for=4.8 citric acid solution
Fe3O4@SBA-15, reaction system are reacted for 24 hours at 50 DEG C.After reaction, biological enzyme is detached by externally-applied magnetic field active force to urge
The chemistry of 50mg is added after system temperature rises to 120 DEG C in agent, the n-butanol that 50mL is then added in the reaction system
Catalyst reacts 8h.In the process gained glucose and 5-HMF calculation of yield method with embodiment 1 the result shows that, urged concatenated
Change reaction system in, glucose yield 87.2%, 5-HMF yields be 44.5%, it was demonstrated that the catalytic performance of the catalyst system and catalyzing compared with
It is high.
(4) regenerability is tested
Regenerability analysis test method is the same as embodiment 1.The result shows that：Loss of catalyst activity is relatively low in regenerative process,
During one to five experiment of regeneration, the yield of glucose is followed successively by 87.1%, 86.9%, 86.5%, 86.1%, 85.0%,
The yield of 5-HMF is followed successively by 43.8%, 43.0%, 42.4%, 41.5% and 40.7%.
Embodiment 3
(1) preparation of biological enzyme agent
By the FeCl of 6.5g3·6H2The NaAc of O and 40g is added in 200mL ethylene glycol, is ultrasonically formed uniformly mixed molten
Liquid；Then the silicon-based mesoporous molecular sieve SBA-15 after taking 10g to dry is dispersed in above-mentioned solution, under stirring conditions, to mixed
20g PEG are added dropwise in zoarium system, solution after mixing is added in autoclave, after reacting 48h at 300 DEG C,
Obtained solid is washed through water and ethyl alcohol, is collected by centrifugation, and obtains loading the Fe that is magnetic after 120 DEG C of vacuum drying3O4SBA-15
(Fe3O4@SBA-15)。
Take Fe obtained by 100mg previous steps3O4@SBA-15 are dispersed in 10mL, in the buffer solution of pH=4.8 citric acids, mix
After closing uniformly, the cellulase of 5.0mg is added into mixed system under stirring conditions, reaction system is reacted at 10 DEG C
After 96h, for products therefrom through being collected by centrifugation, 50 DEG C of vacuum drying obtain biological enzyme agent cellulase-Fe3O4@SBA-15。
(2) preparation of chemical catalyst
The silicon-based mesoporous molecular sieve SBA-15s of 10g after drying are dispersed in 600mL n-hexanes, under stirring conditions,
The zirconium-n-propylate of 58.5g is added dropwise into mixed system.Reaction system at 120 DEG C after hydrolyzing 48h, and products therefrom is through steaming
Distilled water washs 3-5 times, zirconium oxide product (the 1ML-Zr@for being dried in vacuo with 120 DEG C and obtaining SBA-15 and loading single layer is collected by centrifugation
SBA-15)。
1ML-Zr@SBA-15 are dispersed in again in 600mL n-hexanes obtained by 10g previous steps, under stirring conditions, to
The zirconium-n-propylate of 28.5g is added dropwise in mixed system.Reaction system at 120 DEG C after hydrolyzing 48h, and products therefrom is through distillation
Water washing 3-5 times is collected by centrifugation and obtains zirconium oxide product (the 2ML-Zr@SBA- that SBA-15 loads two layers with 120 DEG C of vacuum drying
15)。
2ML-Zr@SBA-15 obtained by 1.8g previous steps are immersed in 90mL, in the sulfuric acid solution of 0.25mol/L, leaching
Bubble centrifuges collected product and is placed in Muffle furnace through 150 DEG C of vacuum drying afterwards for 24 hours, with the heating rate of 10 DEG C/min from room temperature
1200 DEG C are increased to, and 10h is kept at a temperature of 1200 DEG C, obtains the 2ML-Zr/SO of SBA-15 loads4 2-Type solid super-strong acid
(2SZ@SBA-15)。
(3) catalytic activity is tested, i.e. biological enzyme agent and chemical catalyst is applied to sequential catalyst degraded cellulose system
The reaction of standby 5-HMF：
Cellulose pre-processes to obtain fiber monomer with embodiment 1 through ILs.10mL is added in 100mg fiber monomers afterwards,
The biological enzyme agent of 100mg is added into the system after mixing for the citric acid solution of pH=6.0
cellulase-Fe3O4@SBA-15, reaction system react 48h at 80 DEG C.After reaction, pass through externally-applied magnetic field active force point
From biological enzyme agent, the isobutanol of 90mL is then added in the reaction system, after system temperature rises to 180 DEG C, is added
The chemical catalyst of 100mg reacts 12h.Gained glucose and 5-HMF calculation of yield method are the same as 1 result table of embodiment in the process
Bright, in concatenated catalystic converter system, glucose yield 85.8%, 5-HMF yields are 43.5%, it was demonstrated that the catalyst system and catalyzing
Catalytic performance it is higher.
(4) regenerability is tested
Regenerability analysis test method is the same as embodiment 1.The result shows that：Loss of catalyst activity is relatively low in regenerative process,
During one to five experiment of regeneration, the yield of glucose is followed successively by 85.5%, 85.1%, 84.5%, 84.1%, 83.0%,
The yield of 5-HMF is followed successively by 43.2%, 43.0%, 42.6%, 42.1% and 40.2%.
The embodiment is the preferred embodiments of the present invention, but present invention is not limited to the embodiments described above, not
Away from the present invention substantive content in the case of, those skilled in the art can make it is any it is conspicuously improved, replace
Or modification all belongs to the scope of protection of the present invention.
Claims (10)
1. a kind of method that catalytic cellulose conversion prepares 5 hydroxymethyl furfural in green solvent system, which is characterized in that including
Following steps：
A, the preparation of biological enzyme agent：
A1, in proportion by iron chloride hydrate FeCl3·6H2O and sodium acetate NaAc are added in ethylene glycol, are ultrasonically formed mixing
Uniform solution；Then the silicon-based mesoporous molecular sieve SBA-15 after drying is taken to be dispersed in above-mentioned solution, under stirring conditions,
Polyethylene glycol PEG is added dropwise into mixed system, is reacted in solution addition autoclave after mixing, reaction terminates
Afterwards, obtained solid is washed through water and ethyl alcohol, is collected by centrifugation, and is dried in vacuo, and obtains loading the Fe that is magnetic3O4SBA-15 be
Fe3O4@SBA-15；
A2, Fe obtained by step A1 is taken3O4@SBA-15 are dispersed in citric acid solution, after mixing, in the condition of stirring
Lower that cellulase cellulase is added into mixed system, reaction system realizes the load of cellulase at a certain temperature, produces
For object through being collected by centrifugation, vacuum drying obtains biological enzyme agent cellulase-Fe3O4@SBA-15；
B, the preparation of chemical catalyst：
B1, the silicon-based mesoporous molecular sieve SBA-15 after drying is taken to disperse in organic solvent, under stirring conditions, to mixture
Hydrolyzable zirconium salt solution is added dropwise in system, after reaction system hydrolysis is complete, products therefrom is washed, is collected by centrifugation, very
Sky is dry, obtains the zirconium oxide product 1ML-ZrO of SBA-15 load single layers2@SBA-15；
B2,1ML-ZrO obtained by step B1 is taken2Silicon-based mesoporous molecular sieve SBA-15 in@SBA-15 alternative steps B1 repeats step B1
In hydrolysis, obtain SBA-15 and load two layers of zirconium oxide product 2ML-ZrO2@SBA-15；
B3, by the 2ML-ZrO obtained by step B22@SBA-15 are immersed in sulfuric acid solution, after immersion, centrifuge collected production
Object, vacuum drying are placed in Muffle furnace, temperature programming to calcination temperature, and calcining obtains the 2ML-ZrO of SBA-15 loads2/
SO4 2-Type solid super-strong acid 2SZ@SBA-15；
C, chemical catalyst made from biological enzyme agent made from step A and step B is applied to sequential catalyst degradation of fibers
Element prepares the reaction of 5-HMF：
C1, biological enzyme agent cellulase-Fe3O4The step of@SBA-15 catalytic degradation fiber monomers obtain glucose：
Cellulose is handled first to obtain fiber monomer through ionic liquid, it is then in proportion that fiber monomer and lemon acid buffering is molten
Liquid is uniformly mixed, and adds biological enzyme agent cellulase-Fe made from step A3O4@SBA-15, catalytic degradation fiber list
Body obtains glucose；
C2, reaction product obtained by step C1 is detached into biological enzyme agent by externally-applied magnetic field active force, obtains reaction system newly；
The step of C3, chemical catalyst 2SZ@SBA-15 catalytic degradation glucose prepare 5-HMF：
A certain amount of alcoholic solvent will be added in reaction system obtained by step C2, after system temperature rises to required temperature, is added
Chemical catalyst made from step B, reaction terminate, and obtain 5-HMF.
2. catalytic cellulose conversion prepares the side of 5 hydroxymethyl furfural in a kind of green solvent system according to claim 1
Method, which is characterized in that in step A1, described SBA-15, FeCl3·6H2O, NaAc, PEG, ethylene glycol ratio be 0.2-10g：
0.1-6.5g：1-40g：0.4-20g：30-200mL；Reaction temperature is 100-300 DEG C, reaction time 6-48h；Vacuum drying
Temperature be 40-120 DEG C.
3. catalytic cellulose conversion prepares the side of 5 hydroxymethyl furfural in a kind of green solvent system according to claim 1
Method, which is characterized in that in step A2, the citric acid solution pH ranging from 2.0-4.8；The Fe3O4@SBA-15、
Cellulase, citric acid solution ratio be 10-100mg：0.4-5.0mg：1-10mL；Reaction temperature is 0-10 DEG C, instead
It is 12-96h between seasonable；Vacuum drying temperature is 20-50 DEG C.
4. catalytic cellulose conversion prepares the side of 5 hydroxymethyl furfural in a kind of green solvent system according to claim 1
Method, which is characterized in that in step B1, the organic solvent is n-hexane, hexamethylene, normal propyl alcohol or isopropanol；Hydrolyzable zirconates
For zirconium-n-propylate or zirconium iso-propoxide.
5. catalytic cellulose conversion prepares the side of 5 hydroxymethyl furfural in a kind of green solvent system according to claim 1
Method, which is characterized in that in step B1, the SBA-15, hydrolyzable zirconates, organic solvent ratio be 0.2-10g：1.0-
58.5g：10-600mL；Hydrolysising reacting temperature is 50-120 DEG C, reaction time 6-48h；Vacuum drying temperature is 40-120
℃。
6. catalytic cellulose conversion prepares the side of 5 hydroxymethyl furfural in a kind of green solvent system according to claim 1
Method, which is characterized in that in step B2, the 1ML-ZrO2@SBA-15, hydrolyzable zirconates, organic solvent ratio be 0.2-
10g：0.6-28.5g：10-600mL, hydrolysising reacting temperature are 50-120 DEG C, reaction time 6-48h；Vacuum drying temperature
It is 40-120 DEG C.
7. catalytic cellulose conversion prepares the side of 5 hydroxymethyl furfural in a kind of green solvent system according to claim 1
Method, which is characterized in that in step B3, the concentration range of the sulfuric acid solution is 0.005-0.25mol/L；The 2ML-ZrO2@
SBA-15, sulfuric acid solution ratio be 0.2-1.8g：10-90mL, soaking time 4-24h；Vacuum drying temperature is 60-
150℃；Heating rate is 1.0-10 DEG C/min, and calcination temperature is 400-1200 DEG C, calcination time 1-10h.
8. catalytic cellulose conversion prepares the side of 5 hydroxymethyl furfural in a kind of green solvent system according to claim 1
Method, which is characterized in that in step C1, the pH=3.6-6.0 of the citric acid solution, the temperature of reaction system catalytic degradation
It is 20-80 DEG C, time 12-48h.
9. catalytic cellulose conversion prepares the side of 5 hydroxymethyl furfural in a kind of green solvent system according to claim 1
Method, which is characterized in that in step C1, the fiber monomer, citric acid solution, biological enzyme agent cellulase-
Fe3O4The amount ratio of@SBA-15 is 20-100mg：1-10mL：20-100mg.
10. catalytic cellulose conversion prepares 5 hydroxymethyl furfural in a kind of green solvent system according to claim 1
Method, which is characterized in that in step C3, the alcoholic solvent is normal propyl alcohol, isopropanol, n-butanol, isobutanol or the tert-butyl alcohol, reaction
System temperature is 80-180 DEG C, reaction time 4-12h；The alcoholic solvent, chemical catalyst 2SZ@SBA-15, step C2 gained
The amount ratio of reaction system solvent is 9-90mL：20-100mg：1-10mL.
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